‫ المجلد الواحد والثالثون‬2008-‫المجلة القطرية للكيمياء‬
National Journal of Chemistry,2008, Volume 31, 439-446
The Quantum Mechanical Calculations of the Vibration Spectra of
the 1- Fluorofulvene and the 2-Fluorofulvene Molecules
J.H. Ali, S.M. Haddawi , A. M. Bashi, and R. T. Haiwal
Chemistry Dept., Science College, Kerbala Univ
Kerbala-IRAQ.
(NJC)
(Received on 1/11 /2007)
(Accepted for publication 9/6 /2008)
Abstract
The thirty fundamental vibration modes along with their corresponding IR
absorption intensities for both of 1- and 2—fluorofulvene molecules were calculated
using the method based on the MINDO/3-FORCES MO model .The assignments of
all of these vibration modes were , also, carried out .The effect of the fluorine atom on
the vibration spectra of the two molecules were studied. It was shown that there is an
effect on the values of the frequencies and the corresponding IR absorption
intensities of the fundamental vibration modes associated with the methylene group
.In 1-fluorofulvene , any one of these normal modes has the higher frequency and, in
some cases, the lower IR absorption intensity values than the corresponding one in
the 2-fluorofulvene. In addition, the thermodynamic functions, Uo, Ho, So, Go , and Ao
for the two molecules were calculated.
Key words:MINDO/3-FORCES ,1- and 2-fluorofulvene molecules, vibration spectra.
‫الخالصة‬
‫امهت اززيممة امساسممية الثالثم ن برفقممة شممدد امتصمماا امشممحة تحممر الحم مراء المقابلممة‬
‫ساسممت دا طريقممة احتمممد‬
‫ت م حسمماا اماممما‬
‫ فلوروفممولن ن و لم‬-2 ‫ فلوروفممولن ن و‬-1 ‫لهم ا اماممما أالهت اززيممة لكممم مممن الج مري ت ن‬
‫ وتمممر د ارسممة تمماث ر ر‬. ‫ أيضمما ت م تش م يا جميممه ه م ا اماممما امهت اززيممة‬.‫فورس م ز‬-3-‫علمما اسمملوا الم اممدو‬
‫تأث ار علا قي التمرددار االهت اززيمة امساسمية وعلما‬
‫ ووجد إن هاا‬. ‫النلور علا الط ف امهتزازي في الجزي ت ن‬
‫فلوروفمولن ن أي واحمد‬-1 ‫ فمي جزي مة‬.‫شدد امتصاا امشحة تحر الحمراء المصاحسة لها في مجموعمة المثلم ن‬
‫الحماالر شمد امتصماا امشمحة تحمر الحممراء‬
o
U,
‫ت حساا الدوال الثرمودا امكية‬
‫من ه ا اماما امعتيادية يمتل التردد امعلا وفي سحم‬
‫ اضافة ل ل‬. ‫ فلوروفولن ن‬-2 ‫امقم مقاراة مه ما ااظرها في جزي ة‬
.‫ للجري ت ن الم كورت ن‬Ho, So, Go , Ao
fluorosubstituted fulvenes is relatively
common ligand in the organometalic ;
the low-valent titanium-pentafulvene
complexes have been prepared(7).
The 1- and 2-fluorofulvene
molecules, Fig.1, were studied
theoretically(8)
, but there is no
reported study concerning their
vibration spectra.
Introduction
Fulvenes
are
a
crossconjugated molecules with some
unique properties (1-3). Their structure
and electronic distribution were
investigated
theoretically(4)
and
(5)
experimentally . The halogenated
substituted fulvenes were used to
improve the octane quality of a fuel for
an internal combustion engines(6) The
439
‫ المجلد الواحد والثالثون‬2008-‫المجلة القطرية للكيمياء‬
National Journal of Chemistry,2008, Volume 31, 439-446
H
H
3
H
H
H
6
6
5
5
F
4
H
6
6
6
6
H
H
4
1
2
3
H
H
1
2
F
a
b
Fig.1:- a ,1-fluorofulvene and b, 2-fluorofulvene molecules
The aim of this study is to calculate the
vibration spectra of the 1-and 2fluorofulvene molecules , investigate
the effect of the fluorine on the
fundamental vibration frequencies, and
their corresponding IR absorption
intensities, associated with the
methylene
group,
and,
finally,
calculate the thermodynamic functions
of these two molecules.
The present study is based on
MINDO/3-FORCES model(9) which
was developed and applied to the
treatment of organic molecules (10-12).
Such treatment yields the equilibrium
geometry and energy values of the
molecules in addition to their
fundamental vibration frequencies
(3N-6) and IR absorption intensities.
MINDO/3-FORCES
model
adopts the pulay forces method(13) to
evaluate the force constants of
molecules which are introduced then to
the Wilson Secular equation of the
following form(14),
 j L j ( F ij  M ij  )  0
Results and Discussion
The
optimized
geometric
parameters of both of 1- and 2fluorofulvene molecules were listed
along with their heats of formation,
 Hf , and with some other physical
properties, table -1 .From this table, it
was shown that the 2-fluorofulvene is
slightly less stable than the other
molecule. On the other hand, the
character table shows that both
molecules belong to Cs point group and
the thirty fundamental vibration al
frequencies are distributed among the
following symmetry species,



 21 A 9 A
30
Where 21A- are in-plane modes and
9A= are out of plane . Also, all these
vibration modes are IR and Raman
active.
The
thirty
fundamental
vibrations of each one of the two
molecules were listed, tables 2 and 3.
Among of these vibrations, seven
modes are associated with the
methylene group. These are the
symmetric and antsymmetric CH2 st.,
the rocking and scissoring in plane
bending , the wagging and twisting out
of plane bending, and finally, the
C=CH2 stretching vibration. In the
absence of any experimental data, our
calculated results were compared well
with that
obtained by the
MINDO/3(15)
and
the
scaled
frequencies were ,in most cases, close
to that of PM3 (16) ones, tables 2 and
3.The C-F frequency is not pure mode;
it mixed slightly with the ring( CCC )
Solution of this equation yields
vibration frequencies (   4 2  2 C 2 )
and vibration mode eigen vector
coefficients, L j .These coefficients are
utilized in evaluating the atomic partial
participation values (APP) (the partial
contribution of each atom to the
molecular vibration), the ir absorption
intensities and in doing the graphical
representation of each of vibration
mode.(10-12).
440
‫ المجلد الواحد والثالثون‬2008-‫المجلة القطرية للكيمياء‬
National Journal of Chemistry,2008, Volume 31, 439-446
motion in 2-fluorofulvene and with
ring(  CH ) motion in the second
molecule. Also, some of ring(  CH ),
ring(  CH ), and ring( CCC ) modes ,
in both of the molecules, are coupled
with the other vibration motions. The
C-C st. vibrations are not completely
pure and they localized along C-C
bonds .On the others hand, the C-H
vibrations are localized along the C-H
bonds.
In this study, we , also,
investigated the effect of the fluorine
atom on the values of the frequencies
and their corresponding IR absorption
intensities
of
the
fundamental
vibrations, associated with the
methylene group, in the 1- and 2fluorofulvene
molecules.
The
correlation of the fundamental
vibrations, associated with the
methylene group, in the two molecules,
was listed in table-4. From this table,
it was shown that each vibration mode,
in the 2-fluorofulvene, has the lower
frequency and, in some cases, the
higher IR absorption intensity than the
corresponding mode in the 1fluorofulvene.This may be attributed to
the inductive effect caused by the
withdrawing F substituent atom. Due
to the closer of F atom to the
methylene in the 1-fluorofulvene
molecule, the inductive effect is the
greater compared with that in the
second molecule. The inductive effect
causes to draw the electrons towards
the F atom, so, this leads to increase
the energy required for vibration
transitions.
The
thirty
fundamental
vibration frequencies for each one of
the two molecules along with the
rotational constants A, B, and C ,
obtained in this study, were used to
calculate the vibration and rotation
contributions to the thermodynamic
functions according to the following
statistical thermodynamic equations,
(17)
,
30
RTX i
o
=
,
U vib 
xi
1
i 1 e
U
o
rot
=1.5RT
X
30
S vib =R  [
o
i 1
e
i
X i 1
- ln(1-e
3
S rot =R[ 2 +ln
8 2 (8 3 I x I y I z )1 / 2 (kT ) 3 / 2
 Xi
)]
o
 3
]
1.44 
,  =1
T
These two contributions along with
the others contributions, for the
translation, electronic, and nuclear
motions, were used to calculate Uo ,Ho
,So , Ao, and Go thermodynamic
functions
of
the
two
molecules,table5.From this table it was
obvious that the more stable molecule;
Xi=
o
1-fluorofulvene, has the lower S than
that of the second molecule. There is
no available experimental data in order
o
to compare our calculated S
,
(18)
However the isomer fluorobenzene ,
which is more stable than the two
molecules,  Hf, =-90.643 kJ mol-1,
has the value of 0.303 kJ mol-1.deg-1
for S
441
o
National Journal of Chemistry,2008, Volume 31, 439-446
‫ المجلد الواحد والثالثون‬2008-‫المجلة القطرية للكيمياء‬
Table -1: The geometric parameters for 1- and 2-fluorofulvene molecules. Bond
lengths in angstrom and bond angle in degree: See fig.1
Geometric parameter
MINDO/3-FORCES*
1-fluorofulvene
2-fluorofulvene
C1 – C2
1.353
1.353
C2 - C3
1.479
1.467
C3 - C4
1.360
1.358
C4 - C5
1.505
1.506
C5 - C1
1.497
1.507
C5 – C6
1.336
1.338
C3 – H3
1.094
1.086
C4 – H4
1.098
1.100
C6 – H5
1.101
1.101
C1 – F(C2-F)
1.365
1.370
99.7
103.1
 C1 C5 C4
109.7
110.4
 C5 C4 C3
111.5
107.0
 C4 C3 C2
103.4
111.4
 C3 C2 C1
115.5
107.8
 C2 C1 C5
118.7
123.8
 C5 C1F(C5C1H1)
122.4
123.2
 C5 C4 H4
128.9
126.9
 C1 C2 H2(C1C2F)
125.6
128.1
 C4 C3 H3
130.4
128.4
 C6 C5 C1
124.1
124.6
 C5C6H6
110.2
110.5
 H6C6H6
-1
 Hf , kJ mol
71.156
72.180
Dipole moment, (  in Debye)
1.658
2.253
HOMO-LUMO, eV
8.556, 0.100
8.788,0.042
* calculated in this work
442
‫ المجلد الواحد والثالثون‬2008-‫المجلة القطرية للكيمياء‬
National Journal of Chemistry,2008, Volume 31, 439-446
Table: 2 The calculated thirty fundamental vibration frequencies (  in cm-1) along
with the corresponding infrared absorption intensities (IR intensities in km. mol-1) , for
the 1-fluorofulvene molecule. The scaled frequencies and the others calculated
frequencies, for the molecule ,were ,also, shown.
PM3
MINDO/3-FORCES*
MINDO/3
Freq.
**
No Freq,
IR intensity,
Freq. cm-1 Xi$
Assignments
cm-1
-1
-1
cm ;
km mol.
Ref.15
Ref.16
a (in plane)
V1
3586(3105) 10.28
3157
3585
14.997 ring (CH st.)
V2
3547(3071) 27.05
3148
3545
14.833 CH2 as. st
V3
3540(3066) 47.2
31.22
3539
14.809 ring(CH st.)
V4
3528(2963) 17.37
3133
3527
14.312 CH2 s.st.
V5
3518(3046) 20.52
3127
3517
14.713 ring (CH st.)
V6
1854(1626) 30.02
1329
1853
7.854 C =CH2 st
V7
1738(1524) 39.44
1875
1737
7.361 ring(C=C st.)
V8
1671(1465) 28.44
1739
1670
7.076 ring(C=C st.)
V9
1349(1349) 27.31
1518
1349
6.516  s CH2 + ring(C-C st.)
V10 1353(1353) 7.611
1397
1332
6.535
ring (CCC st.)
V11 1309(1309) 13.52
1345
1308
6.322 ring (C-C st.) +  s CH2
V12 1181(1181)
6.79
1298
1179
5.704 ring (  CCC)+ring(C-F st.)
V13 1091(1189)
2.54
1178
1091
5.743 ring(  CH)(clockanticlockwise)
6.5
1.14
0.89
4.85
0.46
1102
1071
954
888
798
1067
1008
891
826
637
5.617
4.868
4.313
4.004
3.318
478(515)
0.2
621
473
2.487
ring(  CH)
ring(  CH) +C-F st.
 CH2+ring(  CCC)
ring (  C-F)+  CH2
ring(  CCC)(ring
elongation)
ring (  CCC)
352(379)
1.01
474
352
1.830
 ring
280
189
0.922
ring (  CF)
V14
V15
V16
V17
V18
1067(1163)
1008(1008)
893(893)
829(829)
637(687)
V19
V20
V21
191(191)
1.99
=
a (out of plane)
V22 917(1010)
1.15
V23 824(898)
0.34
V24 757(825)
0.0
V25 738(804)
7.2
V26 645(645)
5.15
V27 575(575)
3.49
V28 408(408)
4.05
V29 265(265)
1.68
V30 139(196)
1.4
s: symmetric, st: stretching,  : in
1039
918
4.878  CH2
975
824
4.337 ring (  CH.)
907
758
3.984 ring(  CH.)
800
739
3.883 ring(  CH.)
692
647
3.115  CH2+ ring (  CH.)
614
576
2.777 ring (  CH.)+  CH2
461
412
1.970 ring(  CC.)
317
264
1.28
ring(  C-F.)+ ring(  CC)
161
140
0.946 CH2 tor.
plane bending, as: antsymmetric,  : out of plane bending, tor:
torsion,  :rocking,  : wagging,:  :twisting , $:Xi = 1.44

T
* calculated in this work ,
**
The value between brackets is the scaled frequency(15)
443
‫ المجلد الواحد والثالثون‬2008-‫المجلة القطرية للكيمياء‬
National Journal of Chemistry,2008, Volume 31, 439-446
Table 3: The calculated thirty fundamental vibration frequencies (  in cm-1) along
with the corresponding infrared absorption intensities (ir intensities in km mol-1) , for
the 2-fluorofulvene molecule. The scaled frequencies and the others calculated
frequencies, for the molecule ,were ,also, shown.
PM3
MINDO/3-FORCES*
Freq.
MINDO/3
No Freq,**
ir intensity,
Xi$
Assignments
-1
cm
ref.15
-1
-1
cm ;
km mol.
Ref.16,
a (in plane)
V1
3581(3101)
7.37
3158
3579
14.978 ring (CH st.)
V2
3569(3091) 20.76
3152
3568
14.930 ring (CH st.)
V3
3542(3067) 32.08
3140
3541
14.814 CH2 as st.)
V4
3527(2963) 18.02
3136
3526
14.312 CH2 s.st.
V5
3516(3045) 24.23
3131
3515
14.708 ring (CH st.)
V6
1836(1610) 13.10
1920
1835
7.776 C =CH2 st
V7
1735(1521) 37.19
1872
1733
7.346 ring(C=C st.)
V8
1673(1467) 3.330
1743
1672
7.086 ring(C=C st.)
V9
1403(1230) 68.72
1524
1401
5.941 ring(C-C st.)
V10 1330(1448) 0.590
1402
1330
6.994  s CH2
V11 1299(1299) 12.18
1343
1298
6.274 ring (C-C st.)
V12 1162(1267) 12.82
1268
1161
6.119 ring (  CH)
V13 1094(1192) 0.44
1184
1094
5.757 ring(  CH)
V14 1035(1128)
0.49
1084
1035
5.448 ring(  CH)
V15 968(1043)
5.82
1069
966
5.037 ring(  CCC)(ring
elongation)
V16 946(946)
4.50
997
942
4.569 ring(  CCC)+ring(C-F)st.
V17 873(988)
1.49
927
873
4.772
 CH2
V18 594(640)
0.64
726
594
3.091 ring(  CCC)(ring
elongation)
V19 478(515)
1.32
620
473
2.487 ring (  CCC)
V20
344(541)
0.46
463
V21
218(218)
1.88
307
=
a (out of plane)
V22 891(981)
2.46
1043
V23 826(900)
0.03
970
V24 782(852)
9.33
908
V25 711(711)
1.01
808
V26 607(607)
0.64
638
V27 571(571)
2.17
609
V28 498(498)
4.89
546
V29 243(243)
2.68
292
V30 134(134)
0.07
155
For abbreviations and symbols, see table 2.
444
344
2.613
 ring
215
1.052
ring (  CF)
893
826
782
712
610
571
500
243
134
4.738
4.437
4.115
3.434
2.931
2.758
2.405
1.173
0.912
 CH2
ring (  CH.)
ring(  CH.)
ring (  CC.)+  CH2
 CH2+ ring (  CC)
ring (  CC)+  CH2
ring(  CC)+ ring(  C-F.)
ring(  C-F.)+ ring(  CC)
CH2 tor.
‫ المجلد الواحد والثالثون‬2008-‫المجلة القطرية للكيمياء‬
National Journal of Chemistry,2008, Volume 31, 439-446
Table 4:-The correlation of the fundamental vibration frequencies,   , cm-1 and
their corresponding ir intensities, km mol-1 associated with the methylene group
in 1-and 2-fluorofulvene molecules.
Type
of 1-fluorofulvene
2-fluorofulvene

-1
-1
vibration
 , cm ( ir , km mol )
  , cm-1 ( ir , km mol-1)
mode
v16, 893(0.89)
v17, 873(1.49)
 CH2
v22,917(1.15)
v22, 891(2.46)
 CH2
v26,645(5.15)
v26 ,607(0.64)
 CH2
v9,1349(27.31)
v10,1330(0.59)
 s CH2
CH2 as. st. v2,3547(27.05)
v3,3542(32.08)
CH2 s.st.
v4,3528(17.37)
v4,3527(18.02)
C=CH2 st.
v6,1854(30.02)
v6,1836(13.02)
CH2 tor.
V30,139(1.4)
V30,134(0.07)
Table 5: The calculated standard thermodynamics functions at 298.12o K for 1and 2-fluorofulvene molecules
Thermodynamics
function
Uo , kJ mol-1
Ho, kJ mol-1
1-fluorofulvene
2-fluorofulvene
15.801
18.279
16.298
18.776
So, kJ mol-1.deg-1
Go, kJ mol-1
Ao, kJ mol-1
0.430
-109.986
-112.464
0.435
-110.832
-113.311
Thanks for Prof. Dr. M. Shanshal for supplying us the MINDO/3-FORCES program
8- S.M. Khalil and H. M. Jarjis, Z.
Naturforsch., 1990, 45a, 799-806
.
9a -S. M. Khalil and M. Shanshal.
Theor. Chem.. Acta., 1977, 46, 23
.
9b-J. H. Ali and M. Shanshal, Z.
Naturforsch., 2003, 58a, 1.
10-D. H, Abed and M. Shanshal,
Arbeitsherich Des institüts Für
theoretische Chemie, Stüttgart,
1990, 27, 389.
11-D. H. Abed, S. f. Al- Saidi and
M. Shanshal, Chim. Acta Turc,
1995, 23, 7.
12a-R. M. Kubba, S. H. Rida and
A. H. Hanoon, National Journal
of chemistry,2005, 17, 60.
12b J.H. Ali, S.M. Haddawi , A. M.
Bashi,
Journal
of
Kerbala
University, 5,1, 90-97, 2007
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‫ المجلد الواحد والثالثون‬2008-‫المجلة القطرية للكيمياء‬